WO2020199079A1 - Composé de type triène conjugué, son procédé de préparation et son utilisation - Google Patents

Composé de type triène conjugué, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2020199079A1
WO2020199079A1 PCT/CN2019/080824 CN2019080824W WO2020199079A1 WO 2020199079 A1 WO2020199079 A1 WO 2020199079A1 CN 2019080824 W CN2019080824 W CN 2019080824W WO 2020199079 A1 WO2020199079 A1 WO 2020199079A1
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WIPO (PCT)
Prior art keywords
compound
reaction
aryl
alkyl
amino
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Application number
PCT/CN2019/080824
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English (en)
Chinese (zh)
Inventor
陈邦池
孙殷卫
王忠元
赖腾
Original Assignee
泸州东方农化有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 泸州东方农化有限公司 filed Critical 泸州东方农化有限公司
Priority to EP19922955.0A priority Critical patent/EP3950665B1/fr
Priority to PL19922955.0T priority patent/PL3950665T3/pl
Priority to AU2019438654A priority patent/AU2019438654B2/en
Priority to CA3135509A priority patent/CA3135509C/fr
Priority to PCT/CN2019/080824 priority patent/WO2020199079A1/fr
Priority to CN201980003950.0A priority patent/CN111108093B/zh
Publication of WO2020199079A1 publication Critical patent/WO2020199079A1/fr
Priority to US17/489,654 priority patent/US11993555B2/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/31—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/11—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/33—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/41—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by carboxyl groups, other than cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention belongs to the field of organic synthesis, and specifically relates to a new conjugated triene compound and a preparation method and application thereof.
  • the present invention provides a novel conjugated triene compound 1, whose structural formula is expressed as follows:
  • This kind of compound 1 with multifunctional groups is expected to be used to synthesize a variety of derivatives with different chemical properties, physical properties, and biological activities after further functional group conversion reactions, and used to produce final products with practical application value, such as weeding.
  • the application of the herbicide is disclosed by patents such as WO9947525, WO0117352, WO2007073933, WO2008049618 and so on.
  • This type of compound 1 has a novel structure and has not been reported in the literature.
  • a novel conjugated triene compound 1, its structural formula is as follows:
  • R 1 , R 2 , R 3 , R 4 , R 5 are independently hydrogen, C1-C10 alkyl, C6-C12 aryl, or heteroaromatic containing 1 or 2 selected from nitrogen, oxygen, and sulfur atoms base;
  • X 1 and X 2 are independently cyano, -COR 6 , and R 6 is hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C12 aryloxy, amino, C1-C10 Alkylamino, C6-C12 arylamino, bis(C1-C10 alkyl)amino, (C1-C10 alkyl)(C6-C12 aryl)amino, bis(C6-C12 aryl)amino, C6-C12 Aryl or heteroaryl groups containing one or two atoms selected from nitrogen, oxygen, and sulfur.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are independently hydrogen, C1-C4 alkyl, or C6-C12 aryl.
  • R 1 and R 3 are hydrogen, R 2 and R 5 are methyl, and R 4 is ethyl.
  • X 1 and X 2 are independently cyano, -COOMe, -COOEt or -CONH 2 .
  • R 1 , R 2 , R 3 , R 4 , R 5 are independently hydrogen, C1-C10 alkyl, C6-C12 aryl, or heteroaromatic containing 1 or 2 selected from nitrogen, oxygen, and sulfur atoms base;
  • X 1 and X 2 are independently cyano, -COR 6 , and R 6 is hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C12 aryloxy, amino, C1-C10 Alkylamino, C6-C12 arylamino, bis(C1-C10 alkyl)amino, (C1-C10 alkyl)(C6-C12 aryl)amino, bis(C6-C12 aryl)amino, C6-C12 Aryl or heteroaryl groups containing one or two atoms selected from nitrogen, oxygen, and sulfur.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are independently hydrogen, C1-C4 alkyl, or C6-C12 aryl.
  • X 1 and X 2 are independently cyano, -COOMe, -COOEt or -CONH 2 .
  • the isomerization reaction can be carried out in one or more of alkali A, such as alkali metal hydroxide, alkali metal alcoholate, alkali metal hydride, alkaline earth metal hydroxide, alkaline earth metal alcoholate, alkaline earth metal hydride Occurs in the presence of species;
  • alkali A such as alkali metal hydroxide, alkali metal alcoholate, alkali metal hydride, alkaline earth metal hydroxide, alkaline earth metal alcoholate, alkaline earth metal hydride Occurs in the presence of species;
  • the molar ratio of base A to compound 2 is 0.8-2.4:1; preferably 1.0-1.2:1.
  • the halogenating reagent is one or more of halogen element such as chlorine gas or liquid bromine, hypohalous acid such as hypochlorous acid or hypobromous acid, sulfonyl halide such as sulfonyl chloride or halogenated sulfoxide such as thionyl chloride, preferably It is chlorine gas, sulfonyl chloride or liquid bromine.
  • the reaction temperature of the dehydrohalogenation reaction is 0-100°C, preferably 50-80°C.
  • Base B can be an inorganic base or an organic base, preferably an organic base such as an organic amine, and more preferably triethylamine.
  • the process of preparing compound 1 from compound 2 from compound 3 can be carried out in a stepwise or "one-pot method" reaction.
  • R 1 , R 2 , R 3 , R 4 , R 5 are independently hydrogen, C1-C10 alkyl, C6-C12 aryl, or heteroaromatic containing 1 or 2 selected from nitrogen, oxygen, and sulfur atoms base;
  • X 1 and X 2 are independently cyano, -COR 6 , and R 6 is hydrogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C12 aryloxy, amino, C1-C10 Alkylamino, C6-C12 arylamino, bis(C1-C10 alkyl)amino, (C1-C10 alkyl)(C6-C12 aryl)amino, bis(C6-C12 aryl)amino, C6-C12 Aryl or heteroaryl groups containing one or two atoms selected from nitrogen, oxygen, and sulfur.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are independently hydrogen, C1-C4 alkyl, or C6-C12 aryl.
  • X 1 and X 2 are independently cyano, -COOMe, -COOEt or -CONH 2 .
  • the temperature of the aromatization reaction is 100-150°C, preferably 110-150°C.
  • the aromatization reaction can be carried out under the action of a catalyst, and the catalyst is one or more of alkali metal halides or alkaline earth metal halides, preferably lithium chloride or sodium chloride.
  • the molar ratio of catalyst to compound 3 is 0.005-2.4:1.
  • R 1 , R 3 are hydrogen
  • R 2 and R 5 are methyl
  • R 4 is ethyl
  • X 1 and X 2 are cyano
  • 2-(2,6-diethyl-4-methylphenyl)malononitrile R 1.
  • R 3 is hydrogen, R 2 and R 5 are methyl, R 4 is ethyl; X 1 and X 2 are cyano)
  • the herbicide 8-(2,6-diethyl) can be further transformed and reacted -4-Methylphenyl)-7-oxo-1,2,4,5-tetrahydro-7H-pyrazole[1,2-d][1,4,5]oxadiazepine -9-Pivalate (Palfentrazone).
  • the present invention has the following remarkable features:
  • the present invention provides a novel conjugated triene compound 1 and its synthesis method
  • This kind of new compound 1 with multifunctional groups can be used to synthesize other valuable compounds, such as herbicide 8-(2,6-diethyl-4-methylphenyl) after further functional group conversion reaction.
  • herbicide 8-(2,6-diethyl-4-methylphenyl) after further functional group conversion reaction.
  • the raw material olefin 2 is prepared by a method known in the art (for example, WO 2018/120094).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un nouveau composé 1 de type triène conjugué, son procédé de préparation et son utilisation. Le composé 1 de type triène conjugué est obtenu par soumission successive d'un composé dérivé d'acide 2-(cyclohexénylène)malonique en tant que matière première à une réaction d'isomérisation, une réaction d'halogénation en présence d'un réactif d'halogénation, et une réaction de déshydrohalogénation à une certaine température. Un dérivé d'acide 2-aryle malonique, obtenu à partir du composé 1 de type triène conjugué au moyen d'une réaction d'aromatisation, peut être utilisé dans la synthèse d'un composé ayant une activité biologique. La présente invention présente les caractéristiques et avantages significatifs suivants : (1) La présente invention concerne un nouveau composé 1 de type triène conjugué et son procédé de synthèse; et (2) un tel nouveau composé ayant des groupes multifonctionnels peut être utilisé pour synthétiser d'autres composés importants au moyen d'une autre réaction de conversion de groupe fonctionnel.
PCT/CN2019/080824 2019-04-01 2019-04-01 Composé de type triène conjugué, son procédé de préparation et son utilisation WO2020199079A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP19922955.0A EP3950665B1 (fr) 2019-04-01 2019-04-01 Composé de type triène conjugué, son procédé de préparation et son utilisation
PL19922955.0T PL3950665T3 (pl) 2019-04-01 2019-04-01 Sprzężony związek trienowy, sposób jego wytwarzania i jego zastosowanie
AU2019438654A AU2019438654B2 (en) 2019-04-01 2019-04-01 Conjugated triene compound, preparation method therefor and use thereof
CA3135509A CA3135509C (fr) 2019-04-01 2019-04-01 Compose de type triene conjugue, son procede de preparation et son utilisation
PCT/CN2019/080824 WO2020199079A1 (fr) 2019-04-01 2019-04-01 Composé de type triène conjugué, son procédé de préparation et son utilisation
CN201980003950.0A CN111108093B (zh) 2019-04-01 2019-04-01 一种共轭三烯类化合物及其制备方法和应用
US17/489,654 US11993555B2 (en) 2019-04-01 2021-09-29 Conjugated triene compound, and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/080824 WO2020199079A1 (fr) 2019-04-01 2019-04-01 Composé de type triène conjugué, son procédé de préparation et son utilisation

Related Child Applications (1)

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US17/489,654 Continuation US11993555B2 (en) 2019-04-01 2021-09-29 Conjugated triene compound, and preparation and application thereof

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WO2020199079A1 true WO2020199079A1 (fr) 2020-10-08

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US (1) US11993555B2 (fr)
EP (1) EP3950665B1 (fr)
CN (1) CN111108093B (fr)
AU (1) AU2019438654B2 (fr)
CA (1) CA3135509C (fr)
PL (1) PL3950665T3 (fr)
WO (1) WO2020199079A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4293626A (en) * 1977-07-25 1981-10-06 Eastman Kodak Company Electrophotosensitive materials for migration imaging processes
JPH04338761A (ja) * 1991-05-15 1992-11-26 Konica Corp 電子写真感光体
WO1999047525A1 (fr) 1998-03-13 1999-09-23 Novartis Ag Derives de 3-hydroxy-4-aryl-5-oxopyrazoline a activite herbicide
WO2001017352A1 (fr) 1999-09-07 2001-03-15 Syngenta Participations Ag Herbicide
WO2007073933A2 (fr) 2005-12-27 2007-07-05 Syngenta Participations Ag Composition herbicide
WO2008049618A2 (fr) 2006-10-27 2008-05-02 Syngenta Participations Ag Compositions herbicides
WO2018120094A1 (fr) 2016-12-30 2018-07-05 泸州东方农化有限公司 Procédé de préparation d'un dérivé d'acide malonique 2-(cyclohexénylène) et son utilisation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA3135508C (fr) * 2019-04-01 2023-08-29 Oriental (Luzhou) Agrochemicals Co., Ltd. Compose diene conjugue halogene, preparation et utilisation associees

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4293626A (en) * 1977-07-25 1981-10-06 Eastman Kodak Company Electrophotosensitive materials for migration imaging processes
JPH04338761A (ja) * 1991-05-15 1992-11-26 Konica Corp 電子写真感光体
WO1999047525A1 (fr) 1998-03-13 1999-09-23 Novartis Ag Derives de 3-hydroxy-4-aryl-5-oxopyrazoline a activite herbicide
WO2001017352A1 (fr) 1999-09-07 2001-03-15 Syngenta Participations Ag Herbicide
WO2007073933A2 (fr) 2005-12-27 2007-07-05 Syngenta Participations Ag Composition herbicide
WO2008049618A2 (fr) 2006-10-27 2008-05-02 Syngenta Participations Ag Compositions herbicides
WO2018120094A1 (fr) 2016-12-30 2018-07-05 泸州东方农化有限公司 Procédé de préparation d'un dérivé d'acide malonique 2-(cyclohexénylène) et son utilisation
CN108264469A (zh) * 2016-12-30 2018-07-10 泸州东方农化有限公司 一种制备2-（亚环己烯基）丙二酸衍生物的方法及其应用

Also Published As

Publication number Publication date
AU2019438654A1 (en) 2021-11-04
US11993555B2 (en) 2024-05-28
US20220024861A1 (en) 2022-01-27
CN111108093A (zh) 2020-05-05
CN111108093B (zh) 2023-01-24
EP3950665A4 (fr) 2022-11-23
EP3950665B1 (fr) 2023-10-04
CA3135509A1 (fr) 2020-10-08
AU2019438654B2 (en) 2022-10-20
EP3950665A1 (fr) 2022-02-09
PL3950665T3 (pl) 2024-04-02
CA3135509C (fr) 2023-10-03

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